Additives to Improve Open-Time and Freeze-Thaw Characteristics of Water-Based Paints and Coatings

ABSTRACT

Waterborne coatings are described having an acceptable balance of properties both during the storage of coating, application and drying. The period in which irregularities in a freshly applied coating can be repaired without resulting in brush marks is referred to as the open time. Aqueous coatings generally employ dispersed high molecular weight polymers as binders. These binders often provide short open times when the coating is dried since the dispersed polymer particles tend to be immobilized quickly in the edge region of an applied coating. As a result, the viscosity of the coating increases rapidly, which leads to a limited window of workability. The instant invention provides additives that are not volatile but that will extend the time that the film is malleable after it is applied without interfering with other attributes, such as the resistance of the coating to freezing while in the can prior to application.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation-in-Part application of U.S. patentapplication Ser. No. 13/792,175 filed Mar. 10, 2013 which, in turn,claims the priority benefit under 35 U.S.C. section 119 of expired U.S.Provisional Patent Application No. 61/609,269 filed on Mar. 10, 2012;both of which are entirety herein incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to the use of a particular family ofalkoxylated compounds and allylglycidy ether derivatives thereof forimproving open time characteristics of aqueous coating compositions suchas paints, alkyd paints, inks and other paper coating compositions.

More specifically, this invention is directed to the use of variousagents as additives to increase the open time and improve thefreeze-thaw stability of water-based latex paint coatings. The agentsfound to cause such improvements were: Tristyrenated phenols reactedwith one or two units of allylglycidyl ether, then ethylene oxide, thenpossibly sulfamic acid to yield an anion, Distyrenated phenols reactedwith one or two units of allylglycidyl ether and then ethylene oxide,Ethoxylated beta naphthol, Dodecyl benzene sulfonic acid neutralizedwith triethanolamine and formulated with a reverse ethyleneoxide/propylene oxide reverse block co-polymer and water.

BACKGROUND

Waterborne paints, inks, and other coatings are used for a multitude ofapplications including interior and exterior coatings for paper, wood,architectural surfaces, and many more. These coatings are composed of anumber of components such as latex, alkyd, or other binders, pigments orother colorants, water, coalescing agents, thickeners, solvents, and anumber of surfactants for various purposes. With strict environmentallegislation requiring the reduction of the amount of Volatile OrganicCompounds (VOC) in coatings, it is desirable to have paint formulationswith little or no VOC content. Common VOC components in paint includecoalescing agents and glycol freeze-thaw stability additives, amongothers. Removing these has resulted in a number of formulation andcomposition challenges. However, due to competitive pressures, low VOCcoatings and paints must maintain or exceed coating performancestandards expected in the industry.

Since waterborne coatings are subject to freezing at low temperaturescommonly experienced in shipping or storage in northern latitudes, thereis significant interest in improving the freeze/thaw stability of latexpaints. As a consequence of reducing or eliminating VOCs in latex paintsdue to government regulations, simple glycols such as propylene glycol(PG), commonly used to help improve freeze/thaw stability, are beingeliminated. Many coalescing solvents such as Texanol (IBT) that are VOCsare also being eliminated requiring softer (lower Tg) latexes to be usedinstead of the traditional harder (high Tg) latexes. Softer latexes havepoorer freeze/thaw stability characteristics than higher Tg latexesfurther increasing the need for non-VOC freeze/thaw stability additives.

For low VOC paint binder latexes, the average Tg is close to or below 0°C. so that little or no coalescent is needed to make a good coatingafter drying. However, latex binders with low Tg often cause grit whensubjected to freeze/thaw cycles as well as exposure to mechanical shear.The resulting coating films are softer and tackier, even after fullydried, and are susceptible to blocking and dirt pick-up effects. Also,such low Tg latex binders and resulting latex paints are not stable, andgel in a cold environmental storage or transportation process.Freeze-thaw stability of low Tg latex binders and low VOC paints iscritically important for transportation, storage, and practicalapplications. Thus, there is a need to develop latex paints and latexparticle dispersions that meet zero or low VOC requirements and at thesame provide excellent mechanical and film performance withoutsacrificing the freeze-thaw stability of those paints. This requiresnon-VOC freeze/thaw stability additives.

In traditional latex binders for architectural coatings, the glasstransition temperature is between about 10° C. to about 40° C. Thesehigher Tg latexes do not suffer from the grit, blocking, and otherproblems that the low Tg latexes do. However, architectural coatingformulations based on them usually need coalescent agents andanti-freeze agents, both of which are typically high-VOC solvents. Thus,there is a need for non-VOC freeze/thaw stability additives for use withhigher Tg latex binders.

Latex freeze-thaw (sometimes herein referred to as “F/T”) stability,including the freezing-thawing process, destabilization mechanism, andpolymer structures, have been extensively studied since 1950. Blackley,D. C., Polymer Lattices-Science and Technology, 2^(nd) Ed., Vol. 1,Chapman & Hall, 1997, gives a comprehensive review of colloidaldestabilization of latexes by freezing. The freezing process starts withthe decrease of temperature, which leads to the formation of icecrystals. The ice crystal structures progressively increase the latexparticle concentration in the unfrozen water. Eventually latex particlesare forced into contact with each other as the pressure of growing icecrystal structures, resulting in particle aggregation or interparticlecoalescence.

To make a stable latex dispersion in aqueous medium or latex paints withfreeze-thaw stability, various approaches have been employed. Theaddition of antifreeze agents, e.g. glycol derivatives, has been appliedto latex paint to achieve freeze-thaw stability. Thus, latex paintsinclude anti-freeze agents to allow the paints to be used even afterthey have been subjected to freezing conditions. Exemplary anti-freezeagents include ethylene glycol, diethylene glycol, and propylene glycol.For a more detailed discussion see Bosen, S. F., Bowles, W. A., Ford, E.A., and Person, B. D., “Antifreezes,” Ullmann's Encyclopedia ofIndustrial Chemistry, 5^(th) Ed., Vol. A3, VCH Verlag, pages 23-32,1985. However, since these simple glycols are VOCs, a low or no VOCrequirement for the formulated paint means that the glycol level has tobe reduced or eliminated.

A number of methods to achieve freeze/thaw stability are known in theart. Farwaha et. al. (U.S. Pat. No. 5,399,617) discloses the use ofcopolymerizable amphoteric surfactants and discloses latex copolymerscomprising the copolymerizable amphoteric surfactants to impartfreeze-thaw stability to the latex paints. Zhao et. al. (U.S. Pat. No.6,933,415 B2) discloses latex polymers including polymerizablealkoxylated surfactants and discloses the low VOC aqueous coatings basedon them have excellent freeze-thaw stability. Farwaha et. al. (U.S. Pat.No. 5,610,225) discloses incorporating a monomer with long polyethyleneglycol structures to achieve stable freeze-thaw latex. Okubo et. al.(U.S. Pat. No. 6,410,655 B2) discloses freeze-thaw stability of latexpolymers including ethylenic unsaturated monomers.

It is well known that certain nonionic surfactants impart varyingdegrees of freeze/thaw stability to latexes; however, the levelsrequired to impart freeze/thaw stability vary as a function of the Tg ofthe polymers and the propylene glycol level. Some of these nonionicsurfactants are disclosed in U.S. Pat. No. 7,906,577 and in U.S. Pat.No. 8,304,479. Some of these can also function as open time extenders.

Another one of the challenges of formulating waterborne coatings isachieving an acceptable balance of properties both during the filmapplication and drying process as well as in the final film. There is acompetition between the requirements for adequate workability time ofthe coating with appropriate film formation and recoat behavior. Theperiod in which irregularities in a freshly applied coating can berepaired without resulting in brush marks is referred to as the opentime, while the period in which a coating can be applied over anexisting paint film without leaving lap marks is deemed the wet edgetime.

Aqueous coatings generally employ dispersed high molecular weightpolymers as binders. These binders often provide short open times whenthe coating is dried since the dispersed polymer particles tend to beimmobilized quickly in the edge region of an applied coating. As aresult, the viscosity of the coating increases rapidly, which leads to alimited window of workability. Small molecule alkylene glycols such asethylene and propylene glycol are routinely incorporated in aqueouscoatings as humectants, but are considered to be VOCs. Thus, there isalso a need for low VOC additives to improve open time and wet edge inaqueous coatings.

As mentioned above, surfactants are common components of waterbornecoating formulations. They have many functions including dispersingpigments, wetting the substrate, improving flow and leveling, etc.However, once the coating has been applied to a substrate the surfactantis no longer needed. In fact, the presence of the surfactant oftendegrades the moisture sensitivity of the coating. Other coatingproperties can be negatively affected as well. This is largely due tothe mobility of the surfactant polymers. For example, locally highconcentrations of surfactant molecules can form in the coating from thecoalescence of surfactant-coated micelle spheres. When the coating isexposed to water, these unbound surfactant molecules can be extractedfrom the coating leaving thin spots or pathways to the substratesurface. This can result in “blushing” and corrosion of the substrate.

Since surfactants have a number of deleterious effects on the finishedcoating and add cost to the coating formulation, minimizing their usewould be desirable. A non-VOC additive that had multiple functions inthe formulation such as imparting freeze/thaw stability, and extendingopen time and wet edge, and improving coalescence, could reduce the costof and improve the performance of the finished coating.

The present invention provides alkoxylated styrenated phenols andnaphthols that have been derivatized with allyl glycidyl ether asadditives to impart WE/OT to Semigloss paints. Note that the study wasdone with acrylic latexes. Different results may be obtained with VinylAcrylic or Vinyl Acetate Ethylene (VAE) latexes since they are morehydrophilic. The “Martha Stewart Paint was a vinyl acrylic according tothe label. Glidden has manufactured the paint under the Martha Stewartlabel until last year. Now, they still manufacture that paint but underthe Glidden Interior Premium Paint (Semigloss) label. The Martha Stewartcolors still work with the paint since it identical to the paint made inthe past.

SUMMARY OF THE INVENTION

The invention relates to a coating composition comprising: (a) at leastone latex polymer; (b) water; and (c) at least one open time andfreeze-thaw additive in an amount effective to increase the open timeand freeze thaw properties of the coating composition the additivehaving the structural formula

where n=2, x=10-12, y=0-10, z=0-10 and t=0-10, BO denotes a moietyderived from butylene oxide and SO denotes a moiety derived from styreneoxide and R is hydrogen or aC₁-C₂₂ alkyl group and wherein the additive is present in an amountgreater than about 0.5% by weight of the polymer.

The invention also provides a coating composition comprising: (a) atleast one latex polymer; (b) water; and (c) at least one open time andfreeze-thaw additive in an amount effective to increase the open timeand freeze thaw properties of the coating composition the additivehaving the structural formula

where n=1-3, x=1-5, y=0-10, z=5-40, W is selected from the groupconsisting of hydrogen and 1M⁺ where Z is selected from the groupconsisting of SO₃ ⁻ and PO₃ ²⁻, and M⁺ is selected from the groupconsisting of Na⁺, K⁺, NH₄ ⁺, or an alkanolamine; and wherein theadditive is present in an amount greater than about 0.5% by weight ofthe polymer.

It is believed that the present invention in part stabilizes the latexparticles using steric effects of larger hydrophobic groups to form aprotective layer on the surfaces of soft latex particles. The largehydrophobic groups adsorbed or grafted onto the latex particles orco-polymerized into the latex particles prevent these latex particlesfrom approaching the surfaces of other soft latex particles and increasethe distance of separation between soft latex particles. The alkylene,e.g., ethylene oxide units from the surfactant of the alkoxylatedcompounds chains also form a layer which interacts with the aqueousmedium.

DESCRIPTION

The instant invention is directed to a coating composition comprising:(a) at least one latex polymer; (b) water; and (c) at least one opentime and freeze-thaw additive in an amount effective to increase theopen time and freeze thaw properties of the coating composition theadditive having the structural formula I:

where n=2, x=10-12, y=0-10, z=0-10 and t=0-10, BO denotes a moietyderived from butylene oxide and SO denotes a moiety derived from styreneoxide and R is hydrogen or a C₁-C₂₂ alkyl group and wherein the additiveis present in an amount greater than about 0.5% by weight of thepolymer.

The invention is further directed to a coating composition comprising:(a) at least one latex polymer; (b) water; and (c) at least one opentime and freeze-thaw additive in an amount effective to increase theopen time and freeze thaw properties of the coating composition theadditive having the structural formula II:

where n=1-3, x=1-5, y=0-10, z=5-40, W is selected from the groupconsisting of hydrogen and 1M⁺ where Z is selected from the groupconsisting of SO₃ ⁻ and PO₃ ²⁻, and M⁺ is selected from the groupconsisting of Na⁺, K⁺, NH₄ ⁺, or an alkanolamine; and wherein theadditive is present in an amount greater than about 0.5% by weight ofthe polymer. Preferably, x=1-3 and more preferably x=1-2.

This compounds of formula I and II provide improvements in water-basedlatex paints. More specifically, the improvements are (1) the increaseof the open time of water based latex paints and (2) the increase in thenumber of times that the paint can be frozen and then thawed before itloses it integrity as a uniform dispersion.

Additional compounds which are useful in providing improved propertiesto the coating compositions of the invention are selected from the groupconsisting of:

where x=5-40 preferably is x=10; y=0-10, preferably is y=0; W isselected from the group consisting of H, sulfate (—SO₃ ⁻M⁺), phosphate(—PO₃H⁻(M)) and carboxylate (OCH₂COO⁻M⁺) where M⁺ is selected from thegroup consisting of Na⁺, K⁺, NH₄ ⁺ and triethanolamine.

The compounds of the invention can be used in a number of ways forimproving open time characteristics, freeze-thaw cycles, as well asdrying time characteristics, of latex binders, paints, inks and othercoatings. The present invention may optionally employ polymerizablereactive alkoxylated monomers as a reactant during emulsionpolymerization to form the latex polymer. The present invention mayemploy one or more surface active alkoxylated compounds of the formula Ior II as a surfactant (e.g., emulsifier) during emulsion polymerizationto form the latex polymer. The present invention also uses compounds ofthe formula I or II as an additive to latex polymer-containingformulations such as coatings, including but not limited to paints; aswell as an additive for adhesives, including but not limited to pressuresensitive adhesives; glues; resins; sealants; inks, including but notlimited to UV inks, conventional inks, hybrid inks, and water-basedinks; and the like.

The invention also provides a latex paint composition which isfreeze-thaw stable with improved open time, wet edge time and dryingtime characteristics.

In an alternate embodiment, the latex coating composition contains anopen time additive in an amount effective to lengthen the open time ofthe composition to greater than 4 minutes, typically greater than 6minutes. In one embodiment, improved open time characteristics meansthat the open time of a coating or adhesive is made greater than 4minutes. In another embodiment, improved open time characteristics meansthat the open time of a coating or adhesive is made greater than 6minutes. In a further embodiment, improved open time characteristicsmeans that the open time of a coating or adhesive is made greater than 8minutes. In another embodiment, improved open time characteristics meansthat the open time of a coating or adhesive is made greater than 10minutes. In alternate embodiment, improved open time characteristicsmeans that the open time of a coating or adhesive is made greater than12 minutes.

The coating compositions of the invention can optionally containadditives such as one or more film-forming aids or coalescing agents.Suitable firm-forming aids or coalescing agents include plasticizers anddrying retarders such as high boiling point polar solvents. Otherconventional coating additives such as, for example, dispersants,additional surfactants (i.e. wetting agents), rheology modifiers,defoamers, thickeners, biocides, mildewcides, colorants such as coloredpigments and dyes, waxes, perfumes, co-solvents, and the like, can alsobe used in accordance with the invention.

The aqueous coating compositions of the invention can be subjected tofreeze-thaw cycles using ASTM method D2243-82 or ASTM D2243-95 withoutcoagulation.

In one preferred embodiment of the invention, the aqueous coatingcomposition is a latex paint composition comprising at least one latexpolymer derived from at least one acrylic monomer selected from thegroup consisting of acrylic acid, acrylic acid esters, methacrylic acid,and methacrylic acid esters and at least one compound of the formula Ior II; at least one pigment and water. As mentioned above, the at leastone latex polymer can be a pure acrylic, a styrene acrylic, a vinylacrylic or an acrylated ethylene vinyl acetate copolymer.

The present invention further includes a method of preparing an aqueouscoating composition by mixing together at least one latex polymerderived from at least one monomer and mixed with a compound of theformula I or II and at least one pigment. Typically, the latex polymeris in the form of a latex polymer dispersion. The additives discussedabove can be added in any suitable order to the latex polymer, thepigment, or combinations thereof, to provide these additives in theaqueous coating composition. In the case of paint formulations, theaqueous coating composition typically has a pH of from 7 to 10.

In this particular invention, the additives were added to the paintafter it was formulated and were mixed in at levels of 0.05%-5.0% usingnon-aggressive blade mixing.

The most preferred compounds were found to be (see the introduction tothe example table for the key to the abbreviations)

POE(16)DSP reacted with one mole of AGEPOE(16)DSP reacted with two moles of AGEPOE(10)TSP reacted with one mole of AGEPOE(10)TSP reacted with one mole of AGE and then sulfatedPOE(10)TSP reacted with two moles of AGEPOE(10)TSP reacted with two moles of AGE and then sulfatedPOE(10) beta naphtholDDBSA formulated with TEA, water and a water soluble reverse blockcopolymer.

Where the abbreviations stand for: F/T=Freeze/thaw, O/T=Open time,DSP=distyrenated phenol, TSP=tristyrenated phenol, POE=polyoxyethylenepolymer chain, AGE=allyl-glycidyl ether and TCDAM=tricyclodecanemonomethanol

EXAMPLES Terms and Abbreviations

-   F/T=Freeze/thaw-   O/T=Open time-   DSP=distyrenated phenol-   TSP=tristyrenated phenol-   POE=polyoxyethylene polymer chain-   AGE=allyl glycidyl ether-   TCDAM=tricyclodecane monomethanol

Test Procedure Descriptions Open-Time Determination

Two stocks of water-based semi gloss latex paints were provided by BehrPaints of California. One was formulated with a standard additive toimprove its open time and the other was formulated without it. Theversion with the additive was tested as the control for the open-timeevaluations. Comparisons of the test agents were made by post-adding theagents at various percentages to aliquots of the version of the paintthat was formulated without additive and then determining the opentimes. The post-additions were made by simple ambient mixing using anoverhead mixer with a two-inch blade turning at 180 rpm.

All open-times were determined using the method outlined in ASTM methodD 7488-10 and the associated method D-5608. Open-time is the length oftime that flaws in a paint film can be smoothed over with a paint brushafter the first coat has been applied. The test method consists ofdrawing down a film of paint at a certain thickness onto a Lenetacontrast sheet and scratching “X” marks in the film at various pointsalong its length. This is followed by conditioning the film and thenattempting to smooth out the “X” marks at various times using a paintbrush that has been presoaked in the paint. The length of time that the“X” marks can be painted smooth is noted for each additive (this is theopen-time) and the longer the time, the better. As an additional check,the length of time that the raised edge of the original paint strip canthe smoothed is also noted as an open time.

Freeze-Thaw Determinations:

Commercially available Martha Stewart Living White/Base 1 interioracrylic latex semi-gloss MSL3011 and Martha Stewart Living White/Base 1interior acrylic latex semi-gloss MSL3011N paints (both having 50 g/LVOC) were found to have no freeze-thaw resistance under the conditionsof ASTM method D2243-95. These paints were used interchangeably as asubstrate to which the various test additives were post-added at variouspercentages. The freeze-thaw test consists of placing a container ofseveral ml of the test paint mixture in a chamber at −18 C for 17 hoursfollowed by allowing it to thaw under ambient conditions for 7 hours. Asample was deemed to pass a cycle if after freezing solid it thawed backto its original uniformity and flow characteristics. If the samplepassed, the test was repeated up to a maximum of five freeze-thawcycles.

The post-addition blends were made by adding the additives to 100 galiquots of paint and blending the mixtures using an overhead metalblade mixer with a 2-inch blade turning at about 180 rpm under ambientconditions.

The control additive for the Freeze-Thaw tests was Rhodoline FT-100(Rhodia) which is a commercially available agent sold as a freeze-thawimprover. The FT-100 is reported to be a tristyrenated phenol with about10 moles of ethylene oxide reacted to it.

Synthesis of Additives to be Evaluated. Additives 3-10 (See Table ofCompositions, Below.)

The hydrophobes were added to a stainless steel autoclave at the levelsshown in the table below, along with potassium hydroxide at catalyticlevels (2-3 grams) and the autoclave sealed and heated to 105 C.Ethylene oxide was then added, at the levels indicated on the table,over the course of several hours. After all of the EO was consumed, thereaction mass was cooled and the catalyst neutralized with the additionof a small amount of acid.

Additives 12-17

Step one: The hydrophobes, TSP or DSP, are added at the levels shown inthe table below to a stainless steel autoclave, along with allylglycidyl ether (AGE) (also at the levels shown) and a catalytic amountof potassium hydroxide (2-3 grams) and the mix heated to 105 C. When allof the AGE was consumed, the reaction mass was cooled, and the productdischarged.

Step 2: The styrenated phenol/AGE adducts from step 1 were then added toanother autoclave and heated to 105 C. Ethylene oxide, at the levelshown in the table below, was then added over the course of severalhours. After all the EO was consumed, the reaction mass was cooled andthe catalyst neutralized with the addition of a small amount of acid.

Step 3 (for Examples 15 and 17): Selected surfactants from steps 1 and 2were sulfated with sulfamic acid and a trace amount of dicyandiamidecatalyst in a glass reactor equipped with a stirrer, thermometer, andreflux condenser by heating to 120 C until the % sulfate was >90%. Theproducts were then isolated as the ammonium salt.

Table of compositions for Additives Hydrophobe AGE EO Sulfamic acid(equiv.)/ (equiv.)/ (equiv)/ (equiv.)/ Terminal Additive (% wgt) (% wgt)(% wgt) (% agt) group (1) (Behr paint blank NA NA NA NA NA for O/T) (2)(Commercial paint NA NA NA NA NA with no F/T) (3) POE(10) TSP TSP (1)/NA (10)/ NA —OH (45.91%) (53.43%) (4) POE(11.5) DSP DSP (1)/ NA (11.5)/NA —OH (32.92%) (56.1%) (5) POE(20)DSP DSP (1)/ NA (20)/ —OH (23.18%)(76.6%) (6) POE(10) Beta Naphthol Beta naphthol (1) NA (10)/ NA —OH(22.92%) (62.93%) (7) POE(10)cydecanol Cydecanol (1)/ NA (10)/ NA —OH(25.35%) (74.43%) (8) POE(10)TCDAM TCDAM (1)/ NA (10)/ NA —OH (27.27%)(72.33%) (9) POE(10)4- 4-cumylphenol (1)/ NA (10)/ NA —OH cumylphenol(32.42%) (67.36%) (10) POE(10)4- 4-tertamylphenol (1)/ NA (10)/ NA —OHtertamylphenol (27.02%) (72.56%) (11) POE(16)DSP-AGE DSP (1)/ (1)/ (16)/NA —OH (27.6%) (16.96%) (61.91%) (12) POE(15)DSP-AGE (2) DSP (1)/ (2)/(15)/ NA —OH (25.8%) (19.5%) (54.68%) (13) POE(10)TSP -AGE TSP (1)/ (1)/(10)/ NA —OH (41.06%) (11.6%) (47.09%) (14) POE(10)TSP-AGE TSP (1)/ (1)/(10)/ (1)/ —OSO3 Sulfated not neutralized (37.32%) (10.55%) (42.8%)(8.98%) (15) POE(10)TSP-AGE (2) TSP (1)/ (2)/ (10)/ NA —OH (36.93%)(20.84%) (41.96%) (16) POE(10)TSP-AGE (2) TSP (1)/ (2)/ (10)/ (1)/—OSO3— Sulfated Not neutralized (33.90%) (19.13%) (38.52%) (8.08%)

Table of Open-Time and Freeze-Thaw Test Results % Additive actives on %Number of Additive Blank for Edge “X” Gloss Additive For cycles AdditiveDescription Open time Time Time 60 deg Freeze-Thaw passed 1 Controlpaint for open time: Behr Semi gloss with ?  4 min..  8 min. 55.8 NA NAstandard additive (Control for open time) 2 Commercially available 0.5% 4 min.  6 min. 58.1 0.5% None Rhodaline FT-100 in Martha 1.0%  4 min. 8 min. 58.7 1.0% None Stewart paint 1.5% 1.5% None (Control forFreeze-Thaw) 2.0%  4 min.  8 min. 63.3 2.0% 5 2.5% 5 3.0% 5 3 POE(10)TSP 0.5% 0.5% None 1.0% 1.0% 5 1.5% 1.5% 5 2.0% 2.0% 5 2.5% 2.5% 5 3.0%3.0% 5 4 POE(11.5) DSP 0.5% 6 min  8 min. 58.6 0.5% None 1.0% 6 min 12min 56.5 1.0% None 1.5% 1.5% None 2.0% 10 min  14 min 60.7 2.0% 5 5POE(20) DSP 0.5% 6 min  10 min. 58.6 0.5% None 1.0% 8 min 14 min 56.51.0% None 1.5% 1.5% None 2.0% 10 min  20 min 60.7 2.0% None 2.5% 2.5%None 6 POE(10) Beta Naphthol 0.5%  4 min.  8 min 0.5% None 1.0%  6 min.10 min 59.6 1.0% 4 2.0% 10 min.  14 min 61.2 2.0% 5 7 POE(10)cydecanol0.5%  4 min.  6 min. 57.2 0.5% None 1.0%  4 min.  8 min. 58.8 1.0% None1.5% 1.5% None 2.0%  6 min.  12 min. 60.6 2.0% None 2.5% 2.5% None 8POE(10)TCDAM 0.5%  4 min.  6 min. 53.4 0.5% None 1.0%  6 min.  6 min.57.2 1.0% None 2.0%  6 min. 10 min 60.0 2.0% None 9 POE(10)4-cumylphenol0.5%  4 min.  8 min. 56.6 0.5% None 1.0%  6 min.  12 min. 55.6 1.0% None1.5% 1.5% None 2.0% 10 min.   18 min. 62.0 2.0% None 2.5% 2.5% None 10POE(10)4-tertamylphenol 0.5% 0.5% None 1.0% 6 min  8 min. 56.9 1.0% None1.5% 1.5% None 2.0%  8 min. 12 min 59.7 2.0% None 2.5% 2.5% None 11POE(16)DSP AGE 0.5% 6 min 10 min 57.3 0.5% * 1.0% 6 min 14 min 59.2 1.0%None 1.5% 1.5% None 2.0% 6 min 12 min 57.0 2.0% None 12 POE(15) DSP AGE(2) 0.5% 6 min  8 min 58.4 0.5% * 1.0% 6 min 10 min 58.5 1.0% None 1.5%1.5% None 2.0% 6 min 10 min 62.7 2.0% 1 13 POE(10) TSP AGE 0.5% 6 min  8min 57.8 0.5% * 1.0% 4 min  6 min 59.7 1.0% None 1.5% 1.5% 5 (#5grainy)2.0% 4 min  6 min 63.9 2.0% 5 14 POE(10) TSP AGE 0.5% 6 min 10 min 57.90.5% Sulfated 1.0% 6 min 10 min 58.7 1.0% None not neutralized 1.5% 1.5%1 2.0% 4 min 12 min 60.5 2.0% 5 15 POE(10) TSP AGE (2) 0.5% 4 min  8 min58.0 0.5% * 1.0% 4 min  5 min 62.2 1.0% None 1.5% 1.5% 5 (#5 grainy)2.0% 4 min  6 min 65.4 2.0% 5 16 POE(10) TSP AGE (2) 0.5% 4 min 10 min58.3 0.5% Sulfated 1.0% 6 min 10 min 60.1 1.0% None Not neutralized 1.5%1.5% 2 2.0% 6 min 10 min 61.9 2.0% 5 ? Indicates that it is not knownwhether the commercial paint has additive or not but it is used as acontrol for comparison purposes.

Example I

Literature teaches that ethoxylated TSP will offer improvements in thefreeze-thaw performance of water-based coating formulations. Comparingadditive 3 to additive 2, we see that the internally made POE(10) TSP isan improvement over the commercial material, being stable to 5 F/Tcycles at 1.0% additive as opposed to 2%.

Example II DSP, with an Appropriate Level of Ethoxylation is asEffective as TSP as a F/T Additive

Additive 4 shows that 2% POE(11.5) DSP is as effective as the commercialTSP derivative control of additive 2 in that they both must be presentat a minimum of 2%, at which level, they both pass five cycles. Thisexample, further, shows that POE(11.5) DSP yields an O/T performance at0.5% additive that is equal to that of the commercial standard.

Example III The Level of Ethoxylation is Important Both to F/T and toO/T Performance of DSP Derivatives

Comparing additive 5 to additive 4, it is evident that excessiveethoxylation damages the freeze-thaw performance while improving theO/T.

Example IV Derivatives of DSP and TSP Other than the Original POE OfferF/T and/or OT Performances Equivalent to Those Shown in Control Tests 1and 2

Additives 11 and 12 indicate that POE(16)DSP reacted with one and twoAGE groups yields an O/T equal to standard of Test 1.

Additives 13 and 15, which are POE(10)TSP reacted with 1 and 2 moles ofAGE respectively, show open times that are equivalent to the O/T resultsof the standard in Test 1 together with F/T results that are extensionscompared to the results of the standard in Test 2.

Additives 14 and 16 use the sulfated versions of additives 13 and 15,respectively and indicate that sulfation yields an extension in the OTperformance but a slight drop in the F/T performance.

Example V There are Additives Other than Either DSP or TSP Derivativesthat Combine Acceptable F/T and O/T Capabilities

Additive 6 compared to additives 1 and 2 indicates that POE(10) betanaphthol causes acceptable open-times and freeze-thaws.

Example VI

Additives 7, 8, 9, and 10, indicate that POE(10) cydecanol,POE(10)TCDAM, POE(10) 4-cumylphenol and POE(10) tert-amylphenol showreasonable O/T performance, compared to the control tests 1 and 2 eventhough F/T performance was diminished. Again, these are non-DSP andnon-TSP agents.

The contents of all references cited in the instant specifications andall cited references in each of those references are incorporated intheir entirety by reference herein as if those references were denotedin the text.

While the many embodiments of the invention have been disclosed aboveand include presently preferred embodiments, many other embodiments andvariations are possible within the scope of the present disclosure andin the appended claims that follow. Accordingly, the details of thepreferred embodiments and examples provided are not to be construed aslimiting. It is to be understood that the terms used herein are merelydescriptive rather than limiting and that various changes, numerousequivalents may be made without departing from the spirit or scope ofthe claimed invention.

Claimed is:
 1. A coating composition comprising: (a) at least one latexpolymer; (b) water; and (c) at least one open time and freeze-thawadditive in an amount effective to increase the open time and freezethaw properties of the coating composition the additive having thestructural formula

wherein n=2, x=10-12, y=0-10, z=0-10 and t=0-10, BO denotes a moietyderived from butylene oxide and SO denotes a moiety derived from styreneoxide and R is hydrogen or a C₁-C₂₂ alkyl group and wherein the additiveis present in an amount greater than about 0.5% by weight of thepolymer.
 2. A coating composition comprising: (a) at least one latexpolymer; (b) water; and (c) at least one open time and freeze-thawadditive in an amount effective to increase the open time and freezethaw properties of the coating composition the additive having thestructural formula

where n=1-3, x=1-5, y=0-10, z=5-40, W is selected from the groupconsisting of hydrogen and Z⁻M⁺ where Z is selected from the groupconsisting of SO₃ ⁻ and PO₃ ²⁻, and M⁺ is selected from the groupconsisting of Na⁺, K⁺, NH₄ ⁺, or an alkanolamine; and wherein theadditive is present in an amount greater than about 0.5% by weight ofthe polymer.
 3. The coating composition of claim 2 wherein said x=1-3.4. The coating composition of claim 2 wherein said x=1-2.
 5. The coatingcomposition of claim 2 wherein said effective amount is 0.5 to 5.0 wt %.6. The coating composition of claim 2 having a pH of 7 to
 10. 7. Thecoating composition of claim 2 further comprising a pigment.
 8. Thecoating composition of claim 2 wherein said latex polymer is selectedfrom the group consisting of styrene acrylic, vinyl acrylic andacrylated ethylene vinyl acetate copolymer.
 9. The coating compositionof claim 2 wherein said latex polymer comprises at least one monomerselected from the group consisting of acrylic acid, acrylic acid ester,methacrylic acid and methacrylic acid ester.
 10. A coating compositioncomprising: at least one latex polymer; water; and at least one additiveselected from the group consisting of:

wherein: x is 5-40; y=0-10; W is selected from the group consisting ofH, —SO₃ ⁻M⁺, —PO₃H⁻M⁺, and OCH₂COO⁻M⁺; and M⁺ is selected from the groupconsisting of Na⁺, K⁺, NH⁴⁺ and triethanolamine.
 11. The coatingcomposition of claim 10 wherein said x is
 10. 12. The coatingcomposition of claim 10 wherein said y is
 0. 13. The coating compositionof claim 10 wherein said effective amount is 0.5 to 5.0 wt %.
 14. Thecoating composition of claim 10 having a pH of 7 to
 10. 15. The coatingcomposition of claim 10 further comprising a pigment.
 16. The coatingcomposition of claim 10 wherein said latex polymer is selected from thegroup consisting of styrene acrylic, vinyl acrylic and acrylatedethylene vinyl acetate copolymer.
 17. The coating composition of claim10 wherein said latex polymer comprises at least one monomer selectedfrom the group consisting of acrylic acid, acrylic acid ester,methacrylic acid and methacrylic acid ester.
 18. The coating compositionof claim 10 wherein said additive is: